ALBERT

Notizen: New Routes to 1H- and 2H-PyrrolesA synthesis of 1H-pyrroles is described starting with pyridine analogues of chalcones and involving the reaction of acetic anhydride with 1-pyrroline-1-oxides. Another route leads from 1-pyrrolines to 2 H-pyrroles via bromination with N-bromosuccinimide and subsequent dehydrobromination in dimethylformamide.

Notizen: The title compound 1 is a further example of an olefinic alcohol that undergoes ether formation under basic conditions (→ 3) although the double bond is not activated by an electron-attracting group. This unusual reactivity is due to steric compression, which is increased in the 10-methyl analogue 2. This forms the corresponding ether 7 at a much higher rate. - In a deuteriated medium, base-catalysed cyclization of 1 gives the exo-deuteriated ether 6, corresponding to trans-addition. - An X-ray structure analysis of 4, the p-nitrobenzoate of 1, is presented.

Notizen: A substitute for the Darzens glycidic ester synthesis for converting unsaturated ketones or aldehydes into the homologated β,γ- or α,β-unsaturated aldehydes employing sulfur ylides is described. The carbonyl group is converted into the unsaturated oxirane which is then rearranged to the new aldehyde. High yields of isomerically pure aldehydes are available by this method and the process is of practical importance in the conversion of β-ionone into the β-C14-aldehyde, a key intermediate in the Isler synthesis of vitamin A. The efficient preparation of α- and β-cyclocitral by the novel process is also described.

Notizen: Six iridoid glucosides have been isolated from Globularia cordifolia by the combination of open column - and high performance liquid chromatography. The structure of the new compound, named globularifolin, and the identity of the others have been established by chemical transformations and spectral evidence of the compounds and their derivatives.

Notizen: The interaction of selected tetramethylpiperidine derivatives with radicals arising from the Norrish-type I cleavage of dibenzyl ketone under oxygen was studied. Product analyses and kinetic studies showed that the investigated sterically hindered piperidine derivatives have a pronounced effect on both the nature and distribution of the products of photolysis of dibenzyl ketone in the presence of oxygen. Observations indicated that the phenylperacetoxyl radical is formed as an intermediate during irradiation and that it interacts with the additives used. Possible mechanisms of the reactions studied are discussed.The observation that oxidation of an isolated double bond by the radicals formed in dibenzyl ketone photolysis under oxygen is strongly inhibited in the presence of the studied sterically hindered amines is discussed in the light of the results presented. The findings are considered in relation to the problem of polymer stabilization.

Notizen: Several attempts to prepare 3-acetyl-5-benzyl-3-pyrrolin-2-one (7) from phenylalanine are described. This goal was only reached formally, because compound 7 exists in the tautomeric form of (Z)-5-benzyl-3-(1′-hydroxyethylidene)-4-pyrrolin-2-one (17) according to the spectral data. The problem of tautomerism in pyrrolinone systems is discussed.

Notizen: Nucleophilic Aminoalkylation with ThiopivalamidesVorläufige Mitt. [1].Of the twelve thioamides 7a-e and 8a-g, only N,N-dimethylthiopivalamide (7a) could be metallated at the CH-group in a-position to the N-Atom. The reagent 9 thus obtained (Table 1) reacts in high yields with primary haloalkanes, with aldehydes, and with non-enolizable ketones (Table 2). As shown in Scheme 1, the products can be hydrolyzed to pivalamides, cleaved to secondary amines, or reduced to neopentylamines (see 18/19, 15/equation (4) and (5), and 16/20, respectively).

Notizen: Excitation spectra of the cations of pentafluorophenol, 2,3,4-trifluorophenol, 2,4,5-trifluorophenol, 2,5-difluorophenol and 3,5-difluorophenol have been obtained by pumping the B̃2 A″ ← X̃2A″ transition with a dye laser. The cations were first produced in their ground states by Penning ionisation using argon metastables. Vibrational frequencies of some of the fundamentals have been inferred for these cations in the B̃2 A″ state from the excitation spectra, and in the X̃2 A″ state from the emission spectra. Possible applications of the reported results are suggested.

Notizen: Synthesis of Polyhalogenated Butyryl Chlorides, Precursors of Pyrethroid HaloketenesThe copper (I)-catalyzed free radical addition of halomethanes to acrylates and the addition of halogenated acetic acid derivatives to fluoro- or chloro-substituted ethylenes affords polyhalogenated butyric acid derivatives. Chlorides of these acids serve as precursors for haloketenes used in efficient syntheses of pyrethroids.

Notizen: The pyrrolidines 2 and 10 were obtained by thermal ene-reactions at +70° and +180° from the (Z)-4-aza-1, 6-diene 1 and from the (E)-4-aza-1, 6-diene 9 in the ratios of 75:25 and 50:50, respectively. On the other hand, these cyclizations proceeded readily in the presence of diethylaluminum chloride at - 78° and - 35° giving in high yield the trans-pyrrolidine 2 from 1 with 100% and from 9 with 89% diastereoselectivity.

Notizen: Low Temperature 13C-NMR. Spectra of 13C- and 6Li-Labelled Chloro-, Bromo-, and Iodo-lithiumcarbenoidsThe 13C-NMR. spectra of tetrahydrofuran solutions of 16 chloro-, bromo-, and iodo-6lithio- and -7lithio-carbenoids with 13C-labelled methane, ethane, ethylene, and cyclopropane C-skeletons have been measured at temperatures around - 100° (for examples see Fig. 1 and 2). Invariably, the exchange of hydrogen or halogen by lithium causes deshielding (Δδ, see Table 1) of the 13C-signal by up to 289 and 434 ppm, respectively, and decrease of 1J (1H, 13C) and 1J(13C,13C) couplings (see Table 2) with the C-atom of up to 104 and 30 Hz, respectively. The 1J(6Li, 13C) and 1J(7Li, 13C) coupling of ca. 17 and 45 Hz, respectively, obtained in ten cases (Table 1) is independant of the substitution pattern of the C-skeleton and of the particular halogen atom.

Notizen: 1H- and 13C-NMR. data are reported for the complexes [Pt(1)L] and [Pt(2)L]; 1 = OC6H4CH = NCH2CH2O, 2 = OC6H4CH = NC6H4O; L = PR3, AsR3, C ≡ N (cyclohexyl), DMSO, pyridine, secondary amine. The molecular structures of [Pt (2) (NHEt2)] (I) and [Pt (2) (PPh3)] (II) have been determined by X-ray analysis. Relevant bond distances for I: Pt-N (amine) = 2.076 Å, Pt-N (imine) = 2.017 Å, Pt-O = 1.992 Å and 2.002 Å; for II: Pt-P = 2.248 Å, Pt-N = 2.064 Å, Pt-O = 1.964 and 2.005 Å. Both the solid and solution state data are interpreted in terms of differences in the trans influence of the ligand L. The question of metal-ligand d-p π back bonding to the imine is discussed.

Notizen: The complexation of primary ammonium salt substrates by macrocyclic polyether receptor molecules provides a general method for studying the nature and stereochemistry of intermolecular interactions. The substrates and receptors are fitted each with one of the interacting units and the resulting effects in the complex are analyzed. The method is used to study the biologically important indole-pyridinium donor-acceptor interaction. The complexes between macrocycles, bearing an indole group in side chains, and pyridinium-ammonium salts display a characteristic charge-transfer band. The absorption coefficients and stability constants have been determined. Competition experiments also provide a new method for measuring the stability constants of macrocycle-ammonium complexes in organic solvents.

Notizen: Aristoserratine, a New Indole Alkaloid from Aristotelia serrata W.R.B. OLIVER and from A. peduncularis (LABILL.) HOOK. F.The new indole alkaloid aristoserratine (2) has been isolated from Aristotelia. Its structure and absolute configuration were elucidated on the basis of spectroscopic data.

Notizen: When the Hammett-Taft equation log (k/ko)=ρq · σ1q is applied to the solvolysis of the 3-substituted propyl bromides 6a-6i in ethanol/water 4:1 (v/v) log k correlates linearly with σ1q except in cases where R exerts an anchimeric effect. The reaction constant ρq for 6 is - 0.12 and is typical for a nucleophilic solvent-assisted ks process at a primary C-atom. The tertiary halides 1 and 3, however, which react with little or no nucleophilic solvent assistance, i.e. by kc processes, lead to larger ρq values of -0.71 and -1.14, respectively. The reaction constant pq is therefore a sensitive gauge for charge development in the transition state for solvolysis of saturated compounds.

Notizen: Reactions of Some 3-Deoxy-3-trifluoroacetamido-D-ribofuranosyl Halides with Mercuric CyanideThe expected 2,5-anhydro-D-allononitrile 11 was obtained when the 2-O-benzoyl-3-deoxy-3-trifluoroacetamido-D-ribofuranosyl bromide reacted with mercuric cyanide, whereas the isomeric 1,2-O (1-cyanoethylidene) derivative was formed from the 2-O-acetylated halide; no reaction occurred when the halide was 2-O-p-nitrobenzoylated.

Notizen: A series of electrically neutral lipophilic di-, tri-, and tetra-amides containing tertiary-amine N-atoms were prepared in order to investigate their selectivity for alkali and alkaline earth metal cations in solvent polymeric membranes. Considerable selectivity changes were observed for membranes incorporating certain of these ligands as compared with ligand-free membranes. A 1:1 cation/ligand complex was isolated from N, N′, N″-triheptyl-N, N′, N″-trimethyl-nitrilotriacetamid and Mg (SCN)2 whereas with Ca (SCN)2 the corresponding 2:3 cation/ligand complex was formed. N, N′, N″, N‴, N‴-tetramethyl-ethylenediaminetetraacetamide yields a 1:1 cation/ligand complex with Mg (SCN)2.

Notizen: Contribution to the Mass Spectral retro-Diels-Alder Reaction: 1,2,3,4-Tetrahydrophenanthrene[1,4-13C]-1,2,3,4-Tetrahydrophenanthrene (1) was synthesized starting from [1,4-13C]-succinic acid. The mass spectral behavior (EI./MS., 70eV) of 1 is very similar to that of tetraline [2] concerning its loss of ethylene from the molecular ion. Similarly the fragmentation reaction of the synthetic precursors, ketones 7 and 8, seems to partly undergo a carbon rearrangement reaction prior to the elimination of ethylene which is unlike to the behavior of α-tetralone.

Notizen: Contributions to the Knowledge of the Corrin Chromophore, X. Reaction of Derivatives of Cobyrinic Acid Heptamethyl Ester with Hypochlorous Acid(Cobalt)-dicyano-, chloro-cyano-, and dichloro-cobyrinic acid heptamethylesters (1, 2 and 3), respectively, as well as their 10-chloro derivatives 4, 5 and 6 react with hypochlorous acid. A report on the structure and some properties of the reaction products 8, 9 and 10 is given.

Notizen: 3β, 19-Epoxy-3 α-methoxy-steroids (e.g. 1, Scheme 1) are converted into the corresponding 3 α-methoxy-19-oxo compounds (e.g. 3) in the presence of boron trifluoride etherate, via an intramolecular hydride ion transfer from C (19) to (3) which is shown to be an equilibrium process. By subjecting the specifically deuteriated (19 S)- and (19 R)-compounds 1b and 1c to this reaction it was shown to be highly stereoselective.

Notizen: Chemically and isotopically pure Al35Cl3 and Al37Cl3 are synthesized from Al (s) and HCl (g). The yield is quantitative and no measurable decrease in isotopic content from HCl to AlCl3 takes place.

Notizen: The UV. irradiation of 17 β-acetoxy-4-oxa-5 α-androst-1-en-3-one (1) yields A,B-diseco-steroids originating from a Norrish I process of the lactone function.

Notizen: Structural Dynamics of Pentadienyl Metal-Compounds Bearing a Terminal Alkyl Substituent: Both ‘Stereoselective’ and ‘Stereodefensive’ Synthesis of a Natural Perfume.The (2Z, 4E)-, (2E, 4Z)- and (2E, 4E)-isomers of 2,4-decadien-1-ol (5) have been obtained with high and predictable stereochemical homogeneity starting from both (Z)- and (E)-1, 4-decadiene. These hydrocarbons were hydroxylated in a reaction sequence consisting of metallation (by means of s-butyllithium or butyllithium/potassium-t-butoxide, giving rise to organometallic intermediates of specific conformation), dimethoxyborylation and oxidation. The different decadienols as well as (2E, 4Z)-2, 4-undecadien-1-ol were converted into the isovalerates, the ester derived from (2E, 4Z)-2, 4-decadien-1-ol being a natural flavor component.

Notizen: Chemical transformation of tricyclo [3.3.0.02,8]octan-3-one (1) have been carried out in order to explore its potential utility as a versatile synthon for polycyclopentanoid terpenes and prostacyclin analogs. Various functionalizations of rings A and B and annulation of a third ring C were achieved in generally high yields. The system provides for a large measure of regio- and stereoselective reaction control.

Notizen: Replacement of lithium or magnesium by titanium can furnish nucleophilic organometallic reagents of high selectivity as exemplified by the title compound 1 (see Tables 1-3).

Notizen: Nucleosides and Nucleotide. Part 15. Synthesis of Deoxyribonucleoside Monophosphates and Triphosphates with 2(1H)-Pyrimidinone, 2(1H)-Pyridinone and 4-Amino-2(1H)-pyridinone as the BasesThe phosphorylation of the modified nucleosides 1-(2′-deoxy-β-D-ribofuranosyl)-2(1 H)-pyrimidinone (Md, 4), 4-amino-1-(2′-deoxy-β-D-ribofuranosyl)-2(1 H)-pyridinone (Zd, 6) and the synthesis of 1-2′-deoxy-β-D-ribofuranosyl-2(1 H)-pyrimidinone-5′-O-triphosphate (pppMd, 1), 1-(2′-deoxy-β-Dribofuranosyl)-2(1 H)-pyridinone-5′-O-triphosphate (pppIId, 2), and 4-amino-1-(2′-deoxy-βD-ribofuranosyl)-2(1 H)-pyridinone-5′-O-triphosphate (pppZd, 3) are described. The nucleoside-5′-monophosphates pMd (5) and pZd (7) were obtained by selective phosphorylation of Md (4) and Zd (6), respectively, using phosphorylchloride in triethyl phosphate or in acetonitril. The reaction of pMd (5) pII d (8) or pZd (7) with morpholine in the presence of DCC led to the phosphoric amides 9, 10 and 11, respectively, which were converted with tributylammonium pyrophosphate in dried dimethylsulfoxide to the nucleoside-5′triphosphates 1, 2 and 3, respectively.

Notizen: Two novel cannabinoid model compounds, (3R, 4R)-Δ1(6)-tetrahydrocannabinol-5″-oic acid (22) and 4″(R, S)-methyl-(3R, 4R)-Δ1(6)-tetrahydrocannabinol-5″-oic acid (23) were synthesized by acid-catalyzed condensation of (+)-trans-p-mentha-2, 8-dien-l-ol (1) with the substituted resorcinols 18 and 19 obtained by a Wittig reaction between 3, 5-bis(benzyloxy)benzaldehyde (7) and methyl 4-bromobutanoate (10) or methyl 4-bromo-2(R, S)-methylbutanoate (11) resp. with subsequent hydrogenation. The resulting methyl esters 20 and 21 were hydrolyzed to give acids 22 and 23.

Notizen: In HSO3F/SO2ClF the β-hydroxy esters Ph-CHOH-CMe2-COOR (1, R=Me, Et) are doubly protonated, then transformed into the fluorosulfates 7 and (partly) into the fluorides 8. At -15°, both 7 and 8 undergo a rearrangement, forming derivatives of Me2C=C(Ph)COOR (2). By labelling 1 with 13C, singly (13C(3)) and doubly (13C(1,3)), it could be shown that exclusively the ROOC groups undergo a 1,2-shift. Compound 2 is also formed in HSO3F/SO2ClF from the isomeric Me2COH-CHPh-COOR (3) by elimination, and less easily from the α-hydroxy ester Ph-CMe2-CHOH-COOR (5) via a phenyl 1,2-shift. Another isomer, Ph-C(OH)Me-CHMe-COOR (4) gives products different from 2.Using more acidic systems containing SbF5, the free carbenium ions 13 (Ph-CH+-CMe2-COOR) can be stabilized; they do not form 2, possibly because of complexation of the ester group with SbF5. The energy profile and the mechanism of the rearrangement 1 → 2 are discussed.

Notizen: It is shown that ligand 1, designed to span trans-positions, under appropriate conditions also gives cis-mononuclear complexes of platinum (II). The structure of cis-[PtCl2 (1)] (2) has been determined by single-crystal X-ray diffraction. The major distortion from square planar coordination is the P-Pt-P angle of 104.8°. Values of valence angles within the bidentate ligand indicate that this part of the molecule is very strained. Two phenyl groups, one on each phosphorus, lie almost parallel to each other separated by ca. 3.2-3.3 Å. The 1H-NMR. data for this compound show that the π-phenyl interactions observed in the solid state occur also in solution. The preparation and NMR.-spectroscopic properties of trans- and cis-[PtH(PPh3) (1)] [BF4] are reported.

Notizen: A Convenient Synthesis of LeucovorinThe synthesis of leucovorin, a 5-formyl-(6R or S)-5,6,7,8-tetrahydropteroyl-L-glutamic acid (II) is described. The L-folic acid was first reduced to (6R, S)-tetrahy-dro-L-folic acid (I); formylation with methyl-formate in DMSO gave directly leucovorin (as a diastereomeric mixture) in good yields. To demonstrate, that the formylation occurred regiospecifically at N (5) and not at N (10), N (10)-nitroso-(6 R, S)-tetrahydro-L-folic acid was formylated under the same conditions. Reductive elimination of the N (10)-nitrosogroup gave the identical leucovorin as in the previous case. The synthetic leucovorin was biologically as active as the natural product with Streptococcus faecalis ATCC 8043 and Pediococcus cerevisiae ATCC 8081.

Notizen: Partial Synthesis and Oncostatic Properties of Pseudotubulosines, Analogues of Emetine and TubulosinePseudotubulosines, structural analogues of emetine and tubulosine, have been synthesized by either Pictet-Spengler or Bischler-Napieralski condensation from dihydrocorynantheal or corynantheidal. Spectral data, cytotoxic and oncostatic properties of these new alkaloids are described.

Notizen: Metabolites of Microorganisms. FerrithiocinThe strain Tü 1998 from Streptomyces antibioticus produces besides the indicator antibiotics β- and γ-rubromycins a new sulfur containing metabolite. This metabolite, called ferrithiocin, has been isolated in the form of a iron complex. The structure 1 of the iron-free compound was elucidated by spectroscopic studies and chemical degradation.

Notizen: The Hydrolysis of 6exo-Substituted 2exo- and 2endo-Norbornyl p-Toluenesulfonates. Norbornane Series. Part 3Hydrolysis of the 6exo-substituted 2exo- and 2endo-norbornyl p-toluenesulfonates 1b-1 and 2b-1, respectively, in 70% dioxane led to different amounts of the following products: Unrearranged 2exo-norbornanols 3 and norbornenes 5, accompanied in somes cases by small amounts of the rearranged Rendo-epimers 4 and 6 and by norticyclenes 7. When the 6exo-substituent was a nucleophilic group as in 1e-1 and 2e-1, various amounts of tricyclic products were also formed by endo-cyclization. These results show that the 2exo- and 2endo-esters 1 and 2, respectively, react by way of different intermediates. In cases where the 6exo-substituent was an n-electron donor, as in 1m-r and 2m-r, quantitative fragmentation to (3-cyclopentenyl)acetaldehyde (13) occurred.

Notizen: The radical cations and anions of naphtho [1,8-cd]-[1,2,6]thiadiazine (1) and 6,7-dihydroacenaphtho [5, 6-cd]-[1,2,6]thiadiazine (2), as well as the radical anion of acenaphtho [5, 6-cd]-[1,2,6]thiadiazine (3) have been characterized by ESR. spectroscopy. The π-spin distributions in the radical cations \documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\oplus \atop \dot{}}$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ 2^{\oplus \atop \dot{}}$\end{document} strongly resemble those in the iso-π-electronic phenalenyl radical. A prominent feature of the radical anions \documentclass{article}\pagestyle{empty}\begin{document}$ 1^{\ominus \atop \dot{}}$\end{document}, \documentclass{article}\pagestyle{empty}\begin{document}$ 2^{\ominus \atop \dot{}}$\end{document} and \documentclass{article}\pagestyle{empty}\begin{document}$ 3^{\ominus \atop \dot{}}$\end{document} is the substantial localization of the π-spin population on the thiadiazine fragment. These findings are satisfactorily accounted for by HMO models using conventional heteroatom parameters.

Notizen: Two new sesquiterpenoids, nakafuran-8 (1) and -9 (8), have been isolated from the marine sponge Dysidea fragilis and from its prey, the nudibranchs Hypselodoris godeffroyana and Chromodoris maridadilus. The structures were established by spectral analysis and chemical transformations. Both compounds possess antifeedant properties when assayed in the laboratory against common reef fishes, Chaetodon spp.

Notizen: The stereospecific cis-hydroxylation of 1-(2,3-dideoxy-β-D-glyceropent-2-enofuranosyl)thymine (1) into 1-β-D-ribofuranosylthymine (2) by osmium tetroxide is described. Treatment of 2′,3′-O, O-isopropylidene-5-methyl-2,5′-anhydrouridine (8) with hydrogen sulfide or methanolic ammonia afforded 5′-deoxy-2′,3′-O, O-isopropylidene-5′-mercapto-5-methyluridine (9) and 2′,3′-O, O-isopropylidene-5-methyl-isocytidine (10), respectively. The action of ethanolic potassium hydroxide on 5′-deoxy-5′-iodo-2′,3′-O, O-isopropylidene-5-methyluridine (7) gave rise to the corresponding 1-(5-deoxy-β-D-erythropent-4-enofuranosyl)5-methyluracil (13) and 2-O-ethyl-5-methyluridine (14).The hydrogenation of 2 and its 2′,3′-O, O-isopropylidene derivative 4 over 5% Rh/Al2O3 as catalyst generated diastereoisomers of the corresponding 5-methyl-5,6-dihydrouridine (17 and 18).

Notizen: Photochemistry of Cyclic Acetals of the 1,3-Dioxa-4,6-cycloheptadiene TypeUV.-irradiation (λ=254 nm) of 3 gives the isomers (E)-5 (4%), (Z)-5 (60%) and 6 (3%). On triplet sensitization (acetone; λ ≥ 280 nm) 3 is converted to (E)-5 (3%), (Z)-5 (7%) and 7 (9%). - The 1π,π*-excitation (λ=254 nm) of 4 yields the isomers 2 (9%), 8 (10%), 9 (34%), 10 (20%) and 11 (3%). On thermolysis (200°) 4 gives 10 (87%) by a Claisen-rearrangement.

Notizen: Photochemistry of Conjugated γ,δ-Epoxyenones: The Influence of a Hydroxy Substituent in ∊-PositionOn 1n, π*- or 1π,π*-excitation (λ ≥ 347 or λ=254 nm), the ε-hydroxy-γ;,δ-epoxyenone 8 undergoes fission of the C(γ)—O bond followed by the cleavage of the C(δ)-C(ε) bond. This hitherto unknown sequence of reactions is evidenced by the structure determination of the new type products 10-17 and 25, including a synthetic proof for 12 and the X-ray analysis of 11 (X-ray data: triclinic P1; a=7,386(2), b=8,904(4), c=9,684(5)Å; α=82,29(4)°, β=74,46(3)°, γ=82,29(3)°; Z=2).The selective 1π,π*-excitation also induces competitive C(γ)-C(δ) bond cleavage to yield the bicyclic acetal 18 and a ketonium-ylide intermediate a, which photochemically forms a carbene b giving the allene 19 and the cyclopropene 20.On 1n,π*-excitation of the acetate 9 the initial C(γ)-O bond fission is, in contrast to the behaviour of the corresponding alcohol 8, followed by a 1,2-methyl shift affording (E/Z)-28 or by a cyclization-autoxidation process yielding the lactone 29.

Notizen: On the Synthesis of Sulfonated Derivatives of 4- and 5-AminoindanBaking the hydrogensulfate salt of 4-aminoindan (1) and 5-aminoindan (2) led, respectively, to 4-aminoindan-7-sulfonic acid (3) and 5-aminoindan-6-sulfonic acid (4). Acid 4 was also obtained by direct sulfonation of 2. 4-Aminoindan-6-sulfonic acid (5) and 6-aminoindan-4-sulfonic acid (6) were prepared by sulfonation of 4-nitroindan (7) and 5-nitroindan (9), respectively, to 4-nitroindan-6-sulfonic acid (8) and 6-nitroindan-4-sulfonic acid (10), followed by a Béchamp-reduction. Treatment of 1 with amidosulfuric acid gave 3, whereas the same reaction with 2 led to a mixture of 4 and 5-aminoindan-4-sulfonic acid (11). Independent synthesis of 11 was achieved by the following sequence of reactions: sulfur dioxide treatment of the diazonium chloride derived from 4-amino-5-nitrodan (13) gave 5-nitroindan-4-sulfonyl chloride (14); hydrolysis to 5-nitroindan-4-sulfonic acid (15), and final reduction. The 4-aminoindan-5-sulfonic acid (16) was synthesized by treatment of 4-amino-7-bromoindan (18) with amidosulfuric acid to give 4-amino-7-bromoindan-5-sulfonic acid (19) followed by hydrogenolysis. Sulfonation of 4-acetyl-amino-7-bromoindan (17) with oleum followed by hydrolysis led to 7-amino-4-bromoindan-5-sulfonic acid (20), the structure of which was confirmed by reductive dehalogenation to 5.

Notizen: This paper deals with the problem of defining, and measuring, the pH inside the water pool (which we define as pHwp) of reverse micelles, i.e. micelles formed by surfactants dissolved in apolar solvents in the presence of minimal amounts of water. The conceptual and experimental difficulties are discussed, and it is argued that no absolute determination of pHwp is possible, mostly because water in the water pools of reverse micelles is a new solvent, for which no standardization of acidity is available. The problem can be approached only on the basis of an empirical acidity scale.An empirical acidity scale for water pools in reverse micelles of bis (2-ethyl-hexyl) sodium sulfosuccinate (AOT) in isooctane has been defined by measuring the 31P-chemical shifts of phosphate buffers. The chemical shifts in bulk water were compared to those found in reverse micelles under the assumption that the pK of phosphate ion is the same in the two systems. It was found that in most cases there was little difference (less than 0.4 pH units) between pHwp and the pH of the starting buffer in bulk water (which we define as pHst). However, this difference between pHwp and pHst may become much larger in certain cases.The difference (pHwp-pHst) is measured under a variety of conditions, and this permits the determination of an operational acidity in the micelle water pools as a function of the pHst with which the aqueous micelles are prepared. The significance of such data for interpreting the behaviour of enzymes confined in the micelles water pool is discussed. Based on the pHwp scale, the apparent pKa of phenol-red and 4-nitrophenol were determined in reverse micelles containing different buffers and different water content. The pKa values obtained were rather sensitive to changes of both these factors, which was taken to signify that organic dies have only a very limited applicability to measure the acidity of the water pools of reverse micelles.

Notizen: On the Pathway of the Catalytic Reduction of 7-MethylpterinThe catalytic hydrogenation of 7-methylpterin (VII) in a neutral solution occurs first by the reduction of the 7,8-double bond (thermodynamically-controlled reaction) followed by the reduction of the 5,6-double bond. On the contrary, in an acidic medium like CF3COOH, the 5,6-double bond is reduced first (kinetically-controlled reaction). The dihydro-intermediate then undergoes a [1,2]-H-rearrangement leading to the formation of the thermodynamically more stable 7-methyl-7,8-dihydropterin (XV) which on further reduction gives 7-methyl-5,6,7,8-tetrahydropterin (VIII). The catalytic reduction of 7-methyl-7,8-dihydropterin (XV) with deuterium gives stereoselectively a sole product with D at C(6) in the equatorial position.

Notizen: 13C-NMR. Spectra of Dicyanohydroquinones and Dicyano-p-benzoquinonesThe 13C-NMR. spectra of 12 dicyanohydroquinones and fully substituted dicyano- and diazido-p-benzoquinones have been measured and assigned by comparison with related benzene and p-benzoquinone derivatives. For p-benzoquinones the influence of the cyano and azido substituents on the chemical shift of the CO-, α- and β-C-atoms has been investigated.

Notizen: Thermal cyclization of the pyrimidine-N-oxide dicarbamate 2 gives a 95:5 mixture of the 2-oxo-2H-[1,2,4]oxadiazolo[2,3-a]- and [2,3-c]pyrimidinecarbamates 3 and 4. An efficient procedure for the conversion of 3 to 4, and vice versa, is described.

Notizen: Polarographic Investigations on Symmetrical Triazacarbocyanine Dyes in MethanolThe reduction mechanism of eleven symmetrical triazacarbocyanine dyes with different heterocycles in methanol (containing lithium chloride or lithium acetate/acetic acid) has been investigated by means of polarography, cyclic oscillopolarography and coulometry.The reduction occurs in a reversible to irreversible two electron transfer step, followed by an irreversible chemical step. Reduction potentials, transfer coefficients and specific currents have been measured and compared with properties measured in acetonitrile.The effect of substituents X has been studied on the compounds 1-ethyl-2-[3-(1-ethyl-6-X-1,2-dihydroquinolin-2-ylidene)-1-triazeno]-6-X-quinolinium tetrafluoroborate 1f(X) and 3-ethyl-2-[3-(3-ethyl-5-X-Δ4-1, 3-thiazolin-2-ylidene)-1-triazeno]-5-X-1, 3-thiazolium tetrafluoroborate 1g(X), and ρ-values of 0.20 and 0.40 V, respectively, have been found.

Notizen: The anion [(OH)3(O)AsCH2As(O)(OH)2] has been trapped in an X-irradiated single crystal of methylene diarsonic acid. The g-tensor and the hyperfine coupling tensors of the two 75As-nuclei have been obtained and the spin densities in the arsenic 4s- and 4p-orbitals determined.

Notizen: Excited singlet states of bicyclobutylene-benzene (2), 1,2:4,5-bis (bicyclo-butylene)benzene (3), 2,3-bicyclobutylene-naphthalene (4), and 1,8-bicyclobutylene-naphthalene (5) are investigated by means of linear dichroic absorption spectroscopy of molecules oriented in stretched polyethylene films and by semiempirical model calculations. The results indicate a strong hyperconjugative impact of the bicyclobutylene group on the aromatic chromophores in these compounds. Valence isomerization to aromatic products is predicted as the preferred photochemical pathway.

Notizen: The hydrogenation of 2′, 3′-O-isopropylidene-5-methyluridine (1) in water over 5% Rh/Al2O3 gave (5 R)- and (5 S)-5-methyl-5, 6-dihydrouridine (2), separated as 5′-O-(p-tolylsulfonyl)- (3) and 5′-O-benzoyl- (5) derivatives by preparative TLC. on silica gel and ether/hexane developments. The diastereoisomeric differentiation at the C(5) chiral centre depends upon the reaction media and the nature of the protecting group attached to the ribosyl moiety.The synthesis of iodo derivatives (5 R)- and (5 S)-4 is also described. The diastereoisomers 4 were converted into (5 R)- and (5 S)-2′, 3′,-O-isopropylidene-5-methyl-2, 5′-anhydro-5, 6-dihydrouridine (7).

Notizen: The Acylation of 5-Amino-1 H-1,2,4-triazoles. A 13C-NMR. StudyThe acylation of 3-substituted-5-amino-1 H-1,2,4-triazoles (1) with methyl chloroformate or dimethylcarbamoyl chloride yielded mainly 1-acyl-5-amino-1,2,4-triazoles (2 and 3). Acylation of 3-methyl-, 3-methoxy- and 3-methylthio-5-amino-1 H-1,2,4-triazole (1b, 1c and 1d) with methyl chloroformate gave up to 10% of the 1-acyl-3-amino-1,2,4-triazoles. For the unsubstituted 5-amino-1,2,4-triazole (1a), a (1:1)-mixture of the 3- and 5-isomers 2a and 4 was obtained in dioxane in the presence of triethylamine. No 4-acylated product was detected in contrast to earlier reports. The structures of the reaction products were determined with the aid of proton coupled 13C-NMR. spectra using the corresponding N-methyl-1,2,4-triazoles as reference compounds.

Notizen: The X-ray crystallographic molecular dimensions and thermal response of the 5, 13-diphenyl-cyclonoa [b]naphthalene 1a, are described.

Notizen: The Photochemistry of Open-Chained 2,6- or 2,7-Dien-Carbonyl CompoundsOn 1n, π*-excitation (λ 〉 347 nm) citral (5) and the methyl ketone 10 isomerize to compounds A (7, 19) and B (6, 20), whereas the phenyl ketone 11 changes into the isomer 24 of type E. Evidence is given that the conversions to A and B may arise from the 3n, π*-state of the 2,6-diene-carbonyl compounds.On 1n, π*-excitation (λ = 254 nm) 5 and 10 yield the isomers A (7, 19) and D (18, 22), but no products of type B. Furthermore, conversion of 10 to the isomer 21 of type C is observed.Selective 1n, π*-excitation (λ = 254 nm) as well as selective 1n, π*-excitation (λ 〉 347 nm) of the 2,7-diene-carbonyl compounds 12 and 13 give rise to isomerization to the compounds F (25, 28), exclusively. The intramolecular [2 + 2]-photocycloadditions are shown to be triplet processes.UV.-irradiation (λ 〉 280 nm) of compounds F (25, 28) furnishes the isomeric products G (26, 29) which photoisomerize to oxetanes of type H (27, 30).

Notizen: Four triterpenoid saponins (1-4) have been isolated from the berries of Hedera helix L. (Araliaceae) by droplet counter-current and preparative liquid chromatography. The structures have been established by FD./MS. and 13C-NMR. spectroscopy. The isolated compounds were found to possess strong molluscicidal activity against the bilharziasis-transmitting snail Biomphalaria glabrata. Saponin 4, identified as hederagenin 3-O-β-D-glucopyranosyl-(1 → 2)-β-D-glucopyranoside, is a new natural product.

Notizen: Synthesis and Photochemistry of 3-(2-Thienyl)-2,2-dimethyl-2H-azirineThe synthesis of 3-(2-thienyl)-2,2-dimethyl-2 H-azirine (1) is described. UV. irradiation of 1 in benzene solution generates the nitrile isopropylide 2 which reacts in a regiospecific manner with activated C, C and C, O double bonds to give 1-pyrrolines and 3-oxazolines, respectively. With chelidonic acid diethyl ester the cycloaddition of 2 to the C, C double bond is preferred.

Notizen: 7,7-Dimethyl-6-methylidenetricyclo[6.2.1.01,5]undec-9-ene (10) has been prepared from allylic alcohol 8 in one step in 16% yield. Selective hydrogenation of 10 with diazene gives the 2-norzizaenes 1a and 11.

Notizen: STO-3G calculations show that the nitrocyclopropyl anion prefers a triplet ground state with a tetrahedral C(α)-atom and a perpendicular orientation of the three-membered ring and the NO2-group, 1-90° (Table 1). This unusual result is in agreement with recent experimental findings of Kai et al. (Helv. Chim. Acta 65, 137 (1982)). Other NO2-anions as well as all CHO-, COOH- and CN-substituted anions 2-12, have singlet ground states 2-0°-12-0° (Table 1), in agreement with copious experimental data (Wagner & Boche, Z. Naturforsch. 37b, 1339 (1982)).

Notizen: A general method for enlargement of carbocyclic rings by the so called zip reaction is given. The Michael adducts of 2-nitrocycloalkanones with 3-oxo-4-pentenoates in the presence of tetrabutylammonium fluoride give in high yield compounds with the ring enlarged by four C-atoms. By this method 7-, 8-, and 12-membered cycloalkanones were converted respectively to 11-, 12-, and 16-membered functionalized carbocycles (see Scheme 2 and 3).

Notizen: Pure alkaline phosphatase (EC 3.1.3.1; 1500 U/mg) was dialyzed at 4° during 168 h against water, 10-4M EDTA or 10-4M o-phenanthroline. During the dialysis, samples were periodically removed and analyzed for metal content and activity. The results indicate that 1 mol of native calf intestinal alkaline phosphatase contains 4 g-atom of zinc and 4 g-atom of magnesium tightly bound, and that both metal ions are necessary for full enzyme activity. The dialyzed, partially demetallized enzyme could be reactivated by the addition of zinc and/or magnesium salts.

Notizen: Stereochemical Correlations between (2R,4′R,8′R)-α-Tocopherol, (25S,26)-Dihydroxycholecalciferol, (-)-(1S,5R)-Frontalin and (-)-(R)-LinalolThe optically active C5- and C4-building units 1 and 2 with their hydroxy group at a asymmetric C-atom were transformed to (-)-(1S,5R)-Frontalin (7) and (-)-(3R)-Linalol (8) respectively; 1 and 2 had been used earlier in the preparation of the chroman part of (2R,4′R,8′R)-α-Tocopherol (6a, vitamin E), and for introduction of the side chain in (25S,26)-Dihydroxycholecalciferol ((25S)-4), a natural metabolite of Vitamin D3. The stereochemical correlations resulting from these converions fit into a coherent picture with those correlations already known from literature and they confirm our earlier stereochemical assignments. A stereochemical assignment concerning the C(25)-epimers of 25,26-Dihydroxycholecalciferol that was in contrast to our findings and that initiated the conversion of 1 and 2 to 7 resp. 8 for additional stereochemical correlations has been corrected in the meantime by the authors [26].

Notizen: With a modification of the cyclization procedure of Richman & Atkins [8] the two macrocycles 1,4,7-tritosyl-11-benzyl-1,4,7,11-tetraazacyclotetradecane (8) and 1,7,11-tritosyl-4-trityl-1,4,7,11-tetraazacyclotetradecane (15) were prepared. After selective cleavage of the benzyl and trityl group, respectively, one obtains the two key products 1,4,7-tritosyl-11-benzyl-1,4,7,11-tetraazacyclotetradecane (9) and 1,7,11-tritosyl-4-trityl-1,4,7,11-tetraazacyclotetradecane (16) which have three N-atoms protected by tosyl groups and one accessible for further reactions.To test some of the possibilities we have alkylated 9 and 16 with iodoacetamide, 1-tosyl-aziridine and acrylonitrile. After detosylation with HBr in glacial acetic acid in the presence of phenol mono-N-functionalized tetraazamacrocycles were thus obtained. The advantage of this synthesis is that the cyclization which is the most difficult step of the whole procedure, has to be done only once, regardless of the nature of the pendant arm. In addition a large number of derivatives can be prepared by varying the alkylation component.With Ni2+, Cu2+ and Zn2+ metal complexes of these new ligands were prepared and their IR. and VIS. spectra studied. In the case of the carbamoyl derivatives 12, 14 and 18 the Cu2+-complexes exist in two forms. Whereas at low pH the carboxamide group of the pendant arm is probably not bound to the metal ion, at high pH after deprotonation it coordinates in one of the axial positions.

Notizen: Tentative Synthesis of ‘Bis(triasterane)’ and Synthesis of the Heterocyclic (Tricyclo[4.4.1.01,6]undeca-3,8-diene-11,11-dimethyl)sulfiteThe synthesis of the bis(triasterane) (1) has been tried; the reaction of ‘isotetraline’ (1,4,5,8-Tetrahydronaphthalene; 2) with diazomalonate yielded the tricyclic systems 5 and 6, and not 4. Hydrolysis of 5 gave the monocarboxylic acid 7, and not the dicarboxylic acid 9. The latter could be obtained from the dibromoderivative 8, but 9 couldn't be converted to the acyl chloride 10. The reduction of 9 with LiAlH4 yielded the crystalline diol 11, which was cyclized with SOCl2 to the heterocycle 12. The spectral data of the new compounds 5, 6, 7, 11 and 12 are reported and discussed.

Notizen: Synthesis of optically active natural carotenoids and structurally related compounds. IV. Synthesis of (3R, 3′R, 6′R)-luteinThe synthesis of (3R, 3′R, 6′R)-lutein (19) according to the building principle C25+C15=C40 is reported utilizing (R)-4-hydroxy-2,6,6-trimethyl-2-cyclohexen-1-one (4) as a readily available key intermediate.

Notizen: Synthesis of Optically Active Natural Carotenoids and Structurally Related Compounds. VIII. Synthesis of (3S,3′S)-7,8,7′,8′-Tetradehydroastaxanthin and (3S,3′S)-7,8-Didehydroastaxanthin (Asterinic Acid)The synthesis of all-trans-(3S,3′S)-3,3′-dihydroxy-7,8, 7′,8′-tetradehydro-β, β-carotene-4,4′-dione (1), of all-trans-(3S,3′S)-3,3′-dihydroxy-7, 8-didehydro-β,β-carotene-4,4′-dione (2) (asterinic acid = mixture of 1 and 2), and of their 9,9′-di-cis- and 9-cis-isomers is reported starting from (4′S)(2E)-5-(4′-hydroxy-2′, 6′,6′-trimethyl-3′-oxo-l′-cyclohexenyl)-3-methyl-2-penten-4-ynal (8). The absolute configuration (3S,3′S) for both components 1 and 2 of asterinic acid ex Asterias rubens is confirmed on the basis of spectroscopic and direct comparison.

Notizen: A detailed study of the biodegradation of one of the fish toxic chlorinated resin acids, 12,14-dichlorodehydroabietic acidThe correct IUPAC-name is 12,14-dichloro-8,9,11,12-tetradehydro-7,8-dihydroabietic acid. (3) is presented. When exposed to the fungus Mortierella isabellina, 3 is converted into a number of hydroxylated and keto derivatives which show low levels of toxicity to fish. These metabolites were isolated and characterized.

Notizen: Zero-current Ion-transport Studies and Potentiometric Measurements on Membranes Containing Chromoionophores for Li+ and UO22+Non-macrocyclic ionophores for Li+ and UO22+ have been substituted with a diphenylmaleimide unit. In membranes the obtained chromoionophores induce the same ion-selectivity and ion-transport behavior as the unsubstituted ligands.

Notizen: Reactivity-structure correlations for anisole and eleven of its substituted derivatives established from bromination rate constants in liquid SO2, unlike observations in water, show the reaction to be highly sensitive to substituent effects, (ρH2O+ = -7.1; ρSO2+ = -10.51). This result is ascribed to the solvation of the methoxy group which decreases the conjugation of para-substituted (ρO+ = -9.70) compared to that of ortho-substituted derivatives (ρP+ = -8.86). The highly solvated transition state lies far from reactants on the reaction coordinate and the positive charge developed in this state is nearly unity.

Notizen: Peptidic model conjugates carrying a single 2-carboxy-4,6-dinitrophenyl haptenic group, and as carbohydrate moieties D-gluconoyl, β-D-mannopyranosyl, 2-deoxy-β-D-glucopyranos-2-yl, or lactobionoyl residues, including the pseudocarbohydrate residue 1,3,4,5-tetrahydroxycyclohexane-1-carbonyl, were synthesized. Conjugates carrying the lactobionoyl of the bis(2-deoxy-β-D-glucopyranos-2-yl) moiety were anaphylactogenic in the guinea pig, passively sensitized against 2-carboxy-4,6-dinitrophenyl antigen.

Notizen: The stereochemical aspects of the intramolecular Ramberg-Bäcklund reaction, i.e. the 1,3-elimination of hydrogen halide followed by sulfur dioxide extrusion, have been studied on the α-bromosulfones of the 1-thiadecalinThroughout this paper ‘1-thiadecalin’ will be used in place of ‘decahydro-1-thianaphthalene’. series. Whereas the cis,exo-bromosulfone 23a containing the ideal W-type arrangement of the reacting atoms undergoes a clean Ramberg-Bäcklund reaction, the trans,exo- and trans,endo-bromosulfones, 24a and 24b, respectively, lead to an α,β-unsaturated sulfone by simple 1,2-elimination of HBr. Application of the Ramberg-Bäcklund reaction to 9-bromo-8-thiabicyclo[5.2.1]decane-8,8-dioxide (17) permits a short synthesis of the Bredt olefin bicyclo[5.1.1]non-1(8)-ene (5), which can be isolated but shows the typical high reactivity of other methylene-bridged (E)-cyclooctenes.

Notizen: Conversion of 2-bromomethylstyrene 22 and benzocyclobutenyl carbamate 28 to the benzophenanthridine alkaloids (±)-chelidonine (1, five steps, 25% from 28) and to (±)-norchelidonine (2, six steps, 24% from 28) are described. The key step 29 → 31 involves a highly regio- and stereocontrolled intramolecular Diels-Alder reaction of the (E)-quinodimethane 30.

Notizen: Dehydrogenation of hydroaromatic compounds with quinones was reinvestigated in the light of recent criticism of the reaction mechanism. Kinetic and spectroscopic evidence shows that disappearance of substrate proceeds at the same rate as the product-forming step. A mechanism consisting in fast formation followed by slow decomposition of an intermediate can be ruled out. The order of reactivities of 1,4-cyclohexadiene (1), 1,4-dihydronaphthalene (8) and 9,10-dihydroanthracene (11) changes in going from benzoquinone to chloranil or 2,3-dichloro-5,6-dicyanobenzoquinone. It is suggested that this behaviour could be due to contribution of CT-complexes or HOMO-LUMO interactions for determining the reactivity of the substrates.

Notizen: Dependence of the Stereoselectivity on the Leaving Group, the Temperature and the Solvent in the Favorskii-Reaction of Enolisable CyclobutanonesThe base-induced contraction of enolisable 2-halocyclobutanones is often not stereoselectiv. The cis/trans-isomer ratio in the cyclopropanecarboxylic acid 9 derived from 2,4-cis-substituted cyclobutanones 7 depends on the nature of the leaving group. In addition, the choice of the base, the temperature and the solvent can profoundly affect the stereoselectivity of the Favorskii-reaction. The use of the p-bromophenylsulphonyloxy group as leaving group and an inhomogenous reaction medium leads exclusively to cis-carboxylic acid 9.

Notizen: Synthesis of Glyceryletherphosphatides, 2nd Communication. Preparation of 2-O-Acetyl-1-O-[(Z)-9-octadecenyl]-sn -glyceryl-3-phosphorylcholin (‘Oleyl-PAF’), of its Enantiomer and Some Analogous, Unsaturated CompoundsSyntheses of the unsaturated glyceroletherphospholipid 1a as an olefin-analog of ‘Platelet Activating Factor’ (PAF) are described together with the methods for the preparation of the enantiomer 1′a, the corresponding ‘lyso compounds’ 1b and 1′b and their positional isomers 21a, 21′a, 26, 26′, 25, 25′ obtained on formally exchanging the attachment site of the functional groups at the glycerol moiety. Structural assignments and optical purity of the compounds are confirmed.

Notizen: Three macrocyclic polyamines [24]ane-N6 1, [32]ane-N8 2 and [27]ane-N6O3 3 of ring size 24, 32 and 27, respectively, have been synthesized. They contain either trimethylenediamine of ethylenediamine units. The acyclic analog 4, as the reference compound, was also prepared. Compounds 1-3 are macrocyclic analogs of natural polyamines and are potential ligands for metal cations as well as, when protonated, for anions. The protonation constants of compounds 1-4 have been determined. They are high enough for compounds 1-4 to be fully protonated in a pH-range close to neutrality, as required for binding of anions of weak acids. The effect of structural features on the protonation constants are briefly discussed in relation to the design of macrocyclic polyamine ligands.

Notizen: Irradiation (λ〉280 nm) of 3-hydroxypyrroles 1 in acetonitrile leads to the formation of 3,3′-bi-3H-pyrroles 2 in reasonable to good yields.

Notizen: On the Course of the Intramolecular Diels-Alder-Reaction of Cyclopentadienes with Olefinic SubstituentsThe 1:3 mixture of 4-bromobicyclo [3.2.0]hept-2-en-6-one and -7-one (1/2), available by N-bromosuccinimide bromination of bicyclo [3.2.0]hept-2-en-6-one, reacted rapidly with the organo-magnesium and -zinc reagents 3, 10a, 10b and 10d by cyclobutanone ring opening and bromide ion expulsion to give the 5-substituted cyclopentadienes 5, 12a, 12b/12c, and 12d as non-isolated intermediates. Further transformation occured in situ either by a direct intramolecular Diels-Alder reaction (path a) or by a [1,5]-H-migration prior to the intramolecular Diels-Alder reaction (path b). The intermediate 5 followed only path a to give the bridged norbornene derivative 7, the intermediates 12a, 12b and 12c followed only path b to give the annellated norbornene derivatives 15a, 15b and 15c, respectively, and the intermediate 12d followed both paths to give the bridged 14d and the annellated norbornene derivative 15d (in the ration of about 1.4:1). These observations are discussed in terms of the relative velocities of [1,5]-H-migrations and intramolecular Diels-Alder reactions. The major conclusions are: (1) bridged norbornene derivatives with a six-membered ring C (such as 14d) can be prepared by an intramolecular Diels-Alder reaction from 5-alkenyl-cyclopentadienes 12, as long as the dienophilic double bond is activated by an appropriate substituent (as in 12d); (2) such 5-alkenyl-cyclopentadienes 12 are available from the reaction of the bromo-bicyclo-heptenones 1/2 with suitable C-nucleophiles 10.

Notizen: Spiro 3-Oxazolines from the 1,3-Dipolar Cycloaddition of Benzonitrilio-2-propanide and 1,4-QuinonesOn irradiation with light of wavelength 290-350 nm, 2,2-dimethyl-3-phenyl-2H-azirine (1b) reacts with 1,4-naphthoquinone to give the 1H-benzo [f]isoindol-4,9-dione (11) (Scheme 3) via cycloaddition of the benzonitrilio-2-propanide (2b) onto the quinone C, C-double bond. With 2-methyl- and 2,3-dimethyl-1,4-naphthoquinone, the nitrile ylide 2b undergoes cycloaddition preferentially onto the C, O-double bond of the quinone, leading to spiro-oxazolines 12 and 14 (Scheme 4). Steric as well as electronic effects can be discussed to explain the observed site selectivity of the cycloaddition.With the 1,4-benzoquinones 15a, 15b, 15d and 15f, nitrile ylide 2b undergoes the 1,3-dipolar cycloaddition exclusively onto the C, O-double bond. The corresponding spiro-oxazolines have been isolated in 17-32% yield. This contrasts with the previously reported results with benzonitrilipo-phenylmethanide (2a), which undergoes cycloaddition to the C, C-double bond of 1,4-benzoquinones (cf. [1]). This difference in the site selectivity of the 1,3-dipolar cycloaddition can be explained with Houk's concept of LUMO-polarization, that is, the stronger nucleophilic dipol 2b polarizes the LUMO of a α,β-unsaturated carbonyl compound more efficient than the less nucleophilic 2a. This leads to a preference of the cycloaddition to the C, O-double bond in the case of 2b.With 2,3-dimethyl- (15c) and 2,3,5,6-tetramethyl-1,4-benzoquinone (15e), nitrile ylide 2b undergoes C, O- as well as C, C-cycloaddition (Schemes 7 and 8).

Notizen: About the Availability of 13C-NMR Substituent Increments in 1,4-Benzo- and 1,4-NaphthoquinonesThe 13C-NMR spectra of a number of substituted 1,4-benzo- and 1,4-naphthoquinones have been obtained and assigned. Effects of CH3-, O-alkyl-, Cl-, NH2- and N3- substituents have been deduced for the quinoid part of the molecules and used for the calculation of 13C-chemical shifts.

Notizen: Flow thermolysis of 2-propynyl propiolate (5) at 580° afforded butatriene (6) (ca. 50%) and, as by-products, 4-methylene-2-cyclobuten-1-one (7), 2-ethynylpropenal (8), 1-penten-4-yn-3-one (9), 4-penten-2-ynal (10) (total ca. 10%), along with some propynal, acetylene, CO2 and CO. In the same way, propiolic acid (1,1-D2)-2-propynyl propiolate (11) led to (1,1-D2)-butatriene (12) and a little 4-((D2)methylene)-2-cyclobuten-1-one (13). A mechanism is proposed for the transformation of 5 into 6 and of 11 into 12, which also accounts for the formation of 7,8,9 and 10, as well as 13. The position of one of the published 13C-NMR signals of butatriene (6) must be revised. Thermolysis of methyl-(1) and ethyl propiolate (2) resulted in small yields of 2-buten-4-olide (3) and 2-penten-4-olide (4).

Notizen: 13C-NMR. Substituent Increments of the Azido-group in 1,4-BenzoquinonesThe empirical substituent increments of the azido-group in 1,4-benzoquinones have been derived from the 13C-NMR. chemical shifts of 2-azido-5-chloro-1,4-benzoquinone. The validity of the obtained values was tested by comparison of the empirical and computed 13C-NMR. chemical shifts of other azido-chloro-1,4-benzoquinones.

Notizen: The synthesis of a large variety of enantiomerically pure substituted reactive cyclopentenes 16, 23, 24 and 28 have been synthesized from the readily available (-)-quinic acid 1. The straightforward strategy involves a high-yielding intramolecular aldolization-dehydration of acyclic 1,6-dialdehydes 13, 18, 19 and 27 obtained by oxidative cleavage of cyclohexanediols 5, 7, 11 and 12, using either lead tetraacetate or triphenylbismuth carbonate. Neither sulfoxide formation nor racemization of the intermediate dialdehydes at the oxygenated chiral centre was observed. Transformation of the thioacetal 25 to the corresponding ketone 26 using phenylselenic anhydride is also described.

Notizen: Photochromism of spiropyrans. Photodegradation of aza-, oxaza-, and thiaza-cyclopentane- and -cyclohexanespiropyransStudy of the photodegradation of saturated azaheterocyclic spiropyrans showed that electron-donor substituents improve, as in the benzoheterocyclic series, the fatigue properties towards. UV. light. The introduction of oxygen or sulfur in the 5- or 6-membered saturated azacycles or the substitution with an orthofused aromatic nucleus have practically no influence on the results of photodegradation. The indolinospiropyrans allow the greatest number of photochromic cycles before falling to half the initial absorbance on photolysis under accurate conditions.

Notizen: Low-Temperature 13C-NMR. Spectroscopy of Organolithium Derivatives. - 13C, 6Li-Coupling, a Powerful Structural InformationThe 13C-NMR. spectra of thirteen lithiated hydrocarbons (1c-13c. Table 2) and of eighteen a-halo-lithium carbenoids (14c-31c, Table 3) have been recorded in donor solvent (R2O, R3N) mixtures at temperatures down to -150°. The organolithium species were generated from singly or doubly 13C-labelled precursors by H/6Li- or Br/6-exchange. - 13C, 6Li-Coupling was observed of all species but those which supposedly contain contact ion pair C,Li-bonds (benzylic and acetylenic derivatives). The multiplicities of the signals are correlated with the degree of aggregation in solution: the triplets of the halocarbenoids must arise from monomers or heteroatom-bridged oligomers, the quintuplets of butyl-, cyclopropyl-, bycyclo[1.1.0]butyl-, vinyl-, and phenyllithium from dimers with planar arrangement of two Li- and two C-atoms, as known from crystal structures (Scheme 3). All 13C, 6Li-couplings are temperature-dependent, dynamic processes cause them to disappear above ca. -70° (Fig. 1-4). - Types of organolithium compounds are categorized according to the change of chemical shift δΔ (H, Li) upon H/Li-substitution, according to the 13C, 6Li-coupling constants ranging from 0 to 17 Hz, and according to the multiplicities which indicate the aggregation: type A are Li-derivatives of alkanes and cycloalkanes, type B are s̰-bonded vinyl, aryl, and alinyl derivatives, type C are a-heterosubstituted (RS, hetero=halogen) organolithium compounds, and type D are π-bonded allylic and benzylic systems (Table 5). The C,Li-distances in the crystal structures of representatives of all four classes are within the small range of 2.18-2.28 Å (cf. Scheme 3). - Some surprising observations and their interpretations and consequences are: (a) butyllithium solutions in THF, THF/TMEDA, and dimethyl ether contain increasing amounts of dimer upon cooling, the equilibrium (tetramer · 4 THF)+4 THF ⇌ 2 (dimer · 4 THF) being shifted to the right (Fig. 1 and Scheme 4); thus, more of a different species is present at low temperatures, with the accompanying changes in reactivity; (b) mixed higher aggregates are formed upon addition of butyllithium to bicyclobutyllithium; these are broken up to dimers upon addition of TMEDA (Tetramethylethylene-diamine) (Fig. 2 and Scheme 5); (c) the solid state, the calculated gas-phase and the solution species of phenyllithium all have dimeric structures, and so do vinyl and cyclopropyl lithium derivatives; the 13C-deshielding observed upon replacement of H by Li on sp2- and sp-C-atoms is related to a polarization of the π-electrons (Table 3, Fig. 3 and Scheme 6); (d) the spectra of halo-lithium carbenoids show three striking features as compared to the C,H-compound: deshielding of up to 280 ppm (Table 3), strong decrease of the coupling constant with 1H- and 13C-nuclei attached to the carbenoid C-atom (Table 4), and a structure-independant, almost constant, large 13C, 6Li-coupling constant of 17 Hz (Table 3); as shown in Scheme 7, these effects might be the consequence of a reduced degree of hybridization of the carbenoid C-atom. - The preparation of the labelled compounds and the generation of solutions of the organolithium compounds for NMR. measurements are described in full detail.

Notizen: From treatment of D-labelled 1, 2exo-, 1, 2endo- and 2endo, 6endo-trimethylene-norbornane (1, 2 and 3, resp.) with aluminum bromide in carbon disulfide, the evidence is gained that a degenerate rearrangement is involved in the admantane rearrangement of both 1 and 2 to 3.

Notizen: The 1,3-dipolar cycloaddition of the C-t-butyloxycarbonyl-N-mannosyl-nitrone 5, formed in situ from the partially protected D-mannose-oxime 3 and the glyoxylate 4, to ethylene gave preferentially the (3S)-N-glycosyl-isoxazolidine 6 which was transformed into the 3-isoxazolidine-carboxylate (L-5-oxaproline ester) 12 and into some derivatives thereof. The (S)-configuration of 12 was proved by chemical correlation with a derivative of L-asparagine. The D-5-oxaproline ester was obtained from the corresponding N-ribosyl-nitrone 24. Two protected dipeptides containing either C-terminal- (28) or N-terminal-5-oxaproline (= Opro) (30) were synthesized. Starting from 12, the analogue 1 of captopril® (2) was prepared and its activity as an inhibitor of the angiotensin-converting-enzyme (ACE) was examined.

Notizen: (3S, 8E)-1,3-Dihydroxy-8-decen-5-one, a Metabolite of Streptomyces fimbriatus (MILLARD and BURR 1926)From the cultures of Streptomyces fimbriatus, strain Tü 2335, the title compound 1 was isolated by solvent extraction, chromatography, and distillation. Its constitution was determined by spectroscopic investigations of 1 and some of its derivatives, and the chirality by transformation to (R)-1,3-isopropylidenedioxy-decane (12); a reference sample of the latter was prepared from (R)-methyl 3-hydroxydecanoate (10). In the equilibrium mixture the keto form 1 predominates the two hemiacetals 2a and 2b. Compound 1 is inactive against bacteria, yeasts and fungi.

Notizen: (Phenacetin)4·2I4·2H2O is triclinic, a = 13.641 (7), b = 12.807 (6), c = 7.201 (3) Å, α = 99.8 (4), b̃ = 86.5 (4), γ = 104.0 (5)°, P1, Z = 1. The ordered crystal structure has been refined to RF = 0.050, using 4173 independent reflections measured on a four-circle diffractometer with MoKa (graphite monochromator) radiation. The crystals are composed of alternating positively and negatively charged slices; each positive slice contains a double layer of stacks of hemi-protonated phenacetin molecules which are H-bonded through their carbonyl groups (d(O - - - O) = 2.432 (4) Å) while each negative slice contains a single layer of I2-4-ions linked in chains along [100] through H-bonds to pairs of water molecules. The axes of the phenacetin stacks are parallel to the planes of the (I2-4·2H2O)-layers. The I2-4-ion is centro-symmetric and can be approximately represented as I-- - - I-I- - - I- (d(I- - - - I) = 3.404 (1) Å; d(I-I) = 2.774 (1) Å). The compound is a pseudo-type A basic salt.

Notizen: The influence of steric compression on electronic structure in polycyclic olefinic alcohols and amines is studied by PE. spectroscopy.The unsubstituted alcohol 2 and amine 7 show PE.-spectroscopic properties that can be reconciled by postulating a predominance of intramolecularly H-bonded species in the gas phase.For the alkylated derivatives 5 and 9, in which H-bonding is precluded, distinct, but only moderate lone-pair double-bond interactions are observed.

Notizen: The [2.2.2]hericene (6), a bicyclo[2.2.2]octane bearing three exocyclic s-cis-butadiene units has been prepared in eight steps from coumalic acid and maleic anhydride. The hexaene 6 adds successively three mol-equiv. of strong dienophiles such as ethylenetetracarbonitrile (TCE) and dimethyl acetylenedicarboxylate (DMAD) giving the corresponding monoadducts 17 and 20 (k1), bis-adducts 18 and 21 (k2) and tris-adducts 19 and 22 (k3), respectively. The rate constant ratio k1/k2 is small as in the case of the cycloadditions of 2,3,5,6-tetramethylidene-bicyclo [2.2.2]octane (3) giving the corresponding monoadducts 23 and 27 (k1) and bis-adducts 25 and 29 (k2) with TCE and DMAD, respectively. Constrastingly, the rate constant ratio k2/k3 is relatively large as the rate constant ratio k1/k2 of the Diels-Alder additions for 5,6,7,8-tetramethylidenebicyclo [2.2.2]oct-2-ene (4) giving the corresponding monoadducts 24 and 28 (k1) and bis-adducts 26 and 30 (k2). The following second-order rate constants (toluene, 25°) and activation parameters were obtained for the TCE additions: 3+TCE→23: k1 = 0.591±0.012 mol-1·l·s-1, ΔH≠=10.6±0.4 kcal/mol, and ΔS≠ = -24.0±1.4 cal/mol·K (e.u.); 23+TCE→25: k2=0.034±0.0010 mol-1·l·s-1, ΔH≠ = 10.6±0.6 kcal/mol, and ΔS≠ = -29.7±2.0 e.u.; 4+TCE→26: k1 = 0.172±0.035 mol-1·l·s-1, ΔH≠ 11.3±0.8 kcal/mol, and ΔS≠ = -24.0±2.8 e.u.; 24+TCE→26: k2 = (6.1±0.2)·10-4 mol-1·l·s-1, ΔH≠ = 13.0±0.3 kcal/mol, and ΔS≠ = -29.5±0.8 e.u.; 6+TCE→17: k1 = 0.136±0.002 mol-1·l·s-1, ΔH≠ = 11.3±0.2 kcal/mol, and ΔS≠ = -24.5±0.8 e.u.; 17+TCE→18: k2 = 0.0156±0.0003 mol-1·l·s-1, ΔH≠ = 10.9±0.5 kcal/mol, and ΔS≠ = -30.1 ± 1.5 e.u.; 18+TCE→19: k3=(5±0.2) · 10-5 mol-1 mol-1 ·l·s-1, ΔH≠ = 15±3 kcal/mol, and ΔS≠ = -28 ± 8 e.u. The following rate constants were evaluated for the DMAD additions (CD2Cl2, 30°): 6+DMAD→20: k1 = (10±1)·10-4 mol-1 · l·s-1; 20+DMAD→21: k2 = (6.5±0.1) · 10-4 mol-1 ·l·-1; 21+DMAD→22: k3 = (1.0±0.1) · 10-4 mol-1 ·l·s-1.The reactions giving the barrelene derivatives 19, 22, 26 and 30 are slower than those leading to adducts that are not barrelenes. The former are estimated less exothermic than the latter. It is proposed that the Diels-Alder reactivity of exocyclic s-cis-butadienes grafted onto bicycle [2.2.1]heptanes and bicyclo [2.2.2]octanes that are modified by remote substitution of the bicyclic skeletons can be affected by changes inthe exothermicity of the cycloadditions, in agreement with the Dimroth and Bell-Evans-Polanyi principle.Force-field calculations (MMPI 1) of 3, 4, 6 and related exocyclic s-cis-butadienes as a moiety of bicyclo [2.2.2]octane suggested single minimum energy hypersurfaces for these systems (eclipsed conformations, planar dienes). Their flexibility decreases with the degree of unsaturation of the bicyclic skeleton. The effect of an endocyclic double bond is larger than that of an exocyclic diene moiety.

Notizen: Attempted Synthesis of Push-Pull DiacetylenesTwo alternative synthesis of push-pull diacetylenes of type 1 (5-amino-2,4-alkadiynals) are investigated. A bromination-dehydrobromination sequence starting with 5-dimethylamino-2,4-pentadienal (2) as well as the application of the well-known Cadiot-Chodkiewicz coupling reaction give new intermediates 3-5, and 7 and 8, respectively, but fail to give the target molecules 1.

Notizen: Ring Transformations of 3-Substituted 5-Trifluoromethyl-1,3,4-thiadiazol-2(3H)-one with NucleophilesThe 3-chlormethyl-5-trifluoromethyl-1,3,4-thiadiazolone 3 undergoes a ring transformation to 3-acylated 2,3-dihydro-1,3,4-thiadiazoles 4 with many nucleophiles. Upon formal replacement of the chloromethyl group in the 3-position of 3 by an extended bromoalkyl chain (→9a-c), the reaction with nucleophiles yields 4-acylated 5,6-dihydro-4H-1,3,4-thiadiazines 10 (from 9a), 4,5,6,7-tetrahydrothiadiazepines 13 (from 9b) and 5,6,7,8-tetrahydro-4H-1,3,4-thiadiazocines 14 (from 9c) by ring enlargement. The 3-propargyl-thiadiazolone 17 rearranges with nucleophiles to 4-acylated 6-methylidene-5,6-dihydro-4H-1,3,4-thiadiazines 18. The structures of the new compounds were elucidated by 1H- and 13C-NMR spectroscopy.

Notizen: On the Mechanism of the α-Alkynone Cyclization: Synthesis and Thermolysis of 1-(1-Methylcyclopentyl)[3-13C]prop-2-ynoneThe relative migratory aptitude of two acetylenic substituents in the α-alkynone cyclization, a thermal conversion of α-acetylenic ketones A to 2-cyclopentenones C, was investigated by isotope-labeling experiments. The α-alkynone [β-13C]-1, specifically labeled with 13C at the β-acetylenic C-atom C(3), was synthesized by an intramolecular Witting reaction (230-300°) of the diacylmethylidenephosphorane [13C]-7. The latter resulted from acylation of methylidenetriphenylphosphorane with the acid chloride 4 to yield the acylmethylidenephosphorane 5, which in turn was formylated with acetic [13C]formic anhydride ([13C]-6.) Upon thermolysis of [β-13C]-1, its label at C(β) was transferred almost exclusively to C(β) of the 2-cyclopentenone moiety in the resulting cyclization product [13C]-2. We conclude that there is a distinct preference for hydrogen migration in the acetylene → alkylidene carbene isomerization (A → B) which precedes the cyclization step (B → C). No evidence was found for a fast reversibility of this isomerization (A ⇄ B) involving both acetylenic substituents.

Notizen: The Synthesis of 2,3,4,5-1H-Tetrahydroimidazo[2,1-b]quinazolin-2,5-diones and analogous 2,3,4,5-1H-Tetrahydroimidazo[1,2-a]thieno[2,3-d] (or [3,2-d])-pyrimidin-2,5-dionesThe syntheses of various imidazo [2, 1-b]quinazolinediones and their thiophene analogs are described.

Notizen: A conformational study was carried out on Boc-(L-Val-D-Val)6-OMe in the crystalline state by X-ray and IR. and by 1H-NMR. in chloroform. The dodecapeptide crystallizes from CHCl3/EtOAc with a left-handed helical structure of the type ↑↓ β5.6, and from CHCl3/MeOH (or MeOH) with a different structure. In chloroform it forms three slowly interconverting species: one is a ↑↓ β5.6 left-handed helical species, and the other two are most likely single-stranded β4.4 helical species of opposite handedness. The double-stranded helical species is predominant in fresh solutions of samples obtained from CHCl3/EtOAc. Because of the slow conversion or formation of this species some hours are needed to reach the conformational equilibrium in chloroform at 25°.

Notizen: Reaction of cobaltocene with cyclopentadiene and air results in the formation of the title compound; its structure has been elucidated by spectroscopic and X-ray methods.

Notizen: Synthesis of ‘Push-Pull’ DiacetylenesThe first synthesis of push-pull diacetylenes of type 1 is described. Reaction of perchlorobutenyne (8) with two equivalents of dialkylamine, followed by dechlorination using two equivalents of butyllithium gives lithio-dialkylamino-diynes 7. Final acylation of these intermediates leads to push-pull diacetylenes 1b-1e in good yields. The method allows the introduction of both push and pull substituents in a simple one-pot-procedure. In addition, 1a is prepared by hydroxymethylation of lithio-morpholino-diyne 7c, followed by oxidation with manganese dioxide in acetone.

Notizen: The 31P{1H}-NMR characteristics of the complexes [HgX2(1)] and [HgX2-(PPh2Bz)2] (X = NO3, Cl, Br, I, SCN, CN) and the solid state structures of the complexes [HgCl2(1)] and [HgI2(1)] (1 = 2,11-bis (diphenylphosphinomethyl)benzo-[c]phenanthrene) have been determined.The 1J(199Hg, 31P) values increase in the order CN 〈 I 〈 SCN 〈 Br 〈 Cl 〈 NO3. The two molecular structures show a distorted tetrahedral geometry about mercury. Pertinent bond lengths and bond angles from the X-ray analysis are as follows: Hg—P = 2.485(7) Å and 2.509 (8) Å, Hg—Cl = 2.525 (8) Å and 2.505 (10) Å, P—Hg—P = 125.6(3)°, Cl—Hg—Cl = 97.0(3)° for [HgCl2(1)] and Hg—P = 2.491 (10) Å and 2.500(11) Å, Hg—I = 2.858(5) Å and 2.832(3) Å, P—Hg—P = 146.0(4)°, I—Hg—I = 116.9(1)° for [HgI2(1)]. The equation, derived previously, relating 1J(199Hg, 31P) and the angles P—Hg—P and X—Hg—X is shown to be valid for 1.

Notizen: Ligand substitution reactions on square-planar platinum (II) complexes of the types trans-[PtRXL2], trans-[PtR(4-PADA)L2][BF4], trans-[PtRX() and trans-[PtR(4-PADA)()][BF4] R=H, Me; X=Cl-, I-; L=PEt3, bis(3-trifluoromethyl-phenyl)benzylphosphine (4), =the trans-spanning 2,11-bis[bis(3-trifluoro-methylphenyl)phosphinomethyl]benzo [c]phenanthrene (3); 4-PADA (=pyridine-4-azo-4′-(N, N-dimethyl)aniline have been studied at 30° using stopped-flow and conventional spectrophotometry, methanol as solvent, and 2.5 × 10-2 M ionic strength (LiClO4 as supporting electrolyte). 4-PADA was used as indicator ligand, as its absorption spectrum differs from those spectra where it is complexed.The expected steric effects of the bulky ligands, especially of 3, on the rates and mechanisms of all the reactions studied are small. All reactions take place by the usual two-term rate law. Noteworthy, for the complexes with the bulky ligands 3 and 4, the direct reaction path with the entering nucleophile is predominant. There is no preference for a solvent or dissociative path. The reactivity order for the hydride complexes is trans-[PtHX (PEt3)2]〈trans-[PtHX(4)2]〈trans-[PtHX (3)]. However, for the corresponding methyl complexes, there is some retardation by ligand 3, probably due to an interaction between the methyl group and the hydrocarbon moiety of 3, which inhibits the fluxional behavior of this ligand. The results have some relevance for the understanding of olefin-insertion reactions of hydride complexes containing these phosphine ligands.